One-dimensional vanadium-based nano-roll as well as preparation method and application thereof
By using vanadium-based MXene as a precursor, octadecylamine or tetradecylamine solution and hydrothermal reaction, one-dimensional nanoscroll materials were prepared, which solved the problem of high-quality nanoscrolls being difficult to apply on a large scale, and achieved low-cost, high-yield nanoscroll preparation and excellent electrochemical performance.
Patent Information
- Application Number
- CN202510239421.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-03-03
- Publication Date
- 2025-09-12
AI Technical Summary
Existing technologies make it difficult to prepare high-quality one-dimensional vanadium-based nanoscrolls at low cost and high yield, which limits their large-scale application in hydrogen storage, sensing, catalysis, and energy storage.
Using vanadium-based MXene as a precursor, octadecylamine or tetradecylamine solution and hydrothermal reaction, one-dimensional nanoscroll materials are prepared by controlling the reaction conditions. Combining the two-dimensional structural characteristics and metastable characteristics of vanadium-based MXene, a one-dimensional nanoscroll structure is prepared.
The low-cost and high-yield preparation of one-dimensional vanadium-based nanoscrolls has been achieved, which have good electrochemical properties, provide electronic structure, surface active sites and ion transport channels, and improve energy storage performance.
Smart Images
Figure FT_1 
Figure FT_2 
Figure FT_3
Abstract
Description
Technical Field
[0001] The present invention belongs to the field of nanomaterial technology and new energy, and specifically relates to a one-dimensional vanadium-based nanoscroll and a preparation method and application thereof. Background Art
[0002] One-dimensional nanoscrolls, a highly attractive class of nanomaterials, have attracted widespread attention in fields such as hydrogen storage, sensing, catalysis, and energy storage. Nanomaterials with one-dimensional scroll structures can be obtained by folding or rolling two-dimensional ultrathin materials in a spiral shape with the help of external stimuli. Compared to nanotubes, nanoscrolls have open ends, open edges, and adjustable interlayer spacing, which endow them with unique physical and chemical properties.
[0003] Common high-quality nanoscroll structures are usually graphene or boron nitride materials. Due to the limitations of mechanical strength and chemical stability, there are few reports on nanoscroll structures assembled from two-dimensional oxides / sulfides / selenides / carbides, etc. The commonly used preparation method is to curl the planar two-dimensional oxide / sulfide nanosheets grown by CVD driven by organic solvent volatilization into a scroll-like structure.
[0004] However, the nanoscrolls prepared by this method are of high quality but are expensive and have low yields, making it difficult to achieve large-scale application. MXene is a material that is derived from MAX phase etching and has a wide range of applications and great development potential. It has diverse elemental compositions, good conductivity, and abundant surface functional groups. More importantly, MXene has a two-dimensional layered structure similar to graphene, so it can achieve a variety of composition and morphological structure control. In addition, morphology control can avoid the self-stacking of two-dimensional MXene materials, greatly unleashing its structural application potential. For example, the hydrophilic groups and capillary tension of MXene surfaces are used to prepare tubular or spherical morphologies (Adv. Funct. Mater. 2020, 30(50), 2005663), and spherical MXene is prepared by template method (Adv. Mater. 2017, 29(37), 1702410). However, in the reported literature, there is little work on one-dimensional morphology control of MXene. Therefore, developing a low-cost, high-yield method for constructing one-dimensional scroll MXene structures to fully realize the application potential of MXene has high research value. Summary of the Invention
[0005] The object of the present invention is to provide a method for preparing a one-dimensional nanoscroll material, wherein the one-dimensional nanoscroll material is composed of vanadium-based compounds such as vanadium carbide, vanadium oxide, vanadium sulfide, and vanadium selenide.
[0006] Another object of the present invention is to provide a method for constructing one-dimensional MXene materials. The preparation method uses vanadium-based MXene as a precursor and fully utilizes the two-dimensional structural characteristics, metastable characteristics and rich surface functional groups of MXene.
[0007] In order to achieve the above-mentioned object of the invention, the present invention adopts the following technical solutions: A method for preparing a one-dimensional nanoscroll material comprises the following steps: (1) Using vanadium-based MXene powder as the precursor phase for the derivatization reaction; (2) preparing a reaction solvent, wherein the reaction solvent is an octadecylamine solution or a tetradecylamine solution; (3) adding the vanadium-based MXene powder in step (1) to the reaction solvent in step (2) and stirring at room temperature for 2-24 hours; (4) Add the desired chemical reagent as a non-metal source to the mixed solution obtained in step (3) and stir at room temperature for 2-24 h; (5) Transferring the mixed solution obtained in step (4) into a reactor and heating the reaction; (6) washing the precipitate obtained in step (5) to remove the residual solution; (7) Drying the precipitate obtained in step (6) to obtain a vanadium-based MXene-derived one-dimensional nanoscroll material.
[0008] The following are preferred technical solutions of the present invention, but are not intended to limit the technical solutions provided by the present invention. Through the following technical solutions, the technical objectives and beneficial effects of the present invention can be better achieved and realized.
[0009] Preferably, the vanadium-based MXene in step (1) is V2C.
[0010] Preferably, the octadecylamine solution in step (2) is a commercially available chemical reagent, and the tetradecylamine solution is prepared by dissolving the tetradecylamine reagent in anhydrous ethanol and then adding deionized water, wherein the concentration of the tetradecylamine solution is 0.05-0.1 g / mL, and the volume ratio of anhydrous ethanol to deionized water is 0.5-1.
[0011] Preferably, the non-metallic source raw material in step (4) is sulfur powder, selenium powder, etc., and a sulfur source, selenium source, etc. can be provided.
[0012] Preferably, the reaction temperature in step (5) is 150-200 o C, the reaction time is 10-72 h, and heating is carried out in a forced air drying oven or a vacuum drying oven.
[0013] Preferably, the washing solvent in step (6) is anhydrous ethanol.
[0014] Preferably, the drying condition in step (7) is 60 o C dry for 12-48 hours.
[0015] Preferably, the above preparation method comprises the following steps: (1) Take 0.05-0.5 g of V2C MXene powder and add it to 30 mL of commercially available octadecylamine solution or 0.05-0.1 g / mL tetradecylamine anhydrous ethanol / water mixed solution, where the volume ratio of anhydrous ethanol to water is 0.5-1; (2) Take sulfur powder and selenium powder in corresponding stoichiometric ratios or add them to the mixed solution in (1) or do not add any other chemical reagents, and stir with a magnetic stirrer until the solution is mixed uniformly; (3) Transfer the mixed solution in step (2) into the reactor, seal it and place it in a vacuum drying oven or a forced air drying oven at 150-200 o C temperature range for 10-72 h; (4) Wash the obtained precipitate with anhydrous ethanol 3-6 times to remove the residual solution; (5) The precipitate obtained in step (4) was heated to 60 o C for 12-48 h.
[0016] The present invention has the following beneficial effects: This method utilizes the ultrathin atomic-layer structure of vanadium-based MXene, its uniformly negatively charged surface functional groups, and thermodynamically metastable metal atoms. Based on the interaction between amine groups and MXene surface functional groups, a one-dimensional vanadium-based nanoscroll structure is prepared via a hydrothermal reaction. This method is simple, easy to control, low-cost, and easy to mass-produce. The prepared one-dimensional vanadium-based nanoscrolls can provide a more beneficial electronic structure, surface active sites, volume expansion space, and ion transport channels when used as negative electrode materials for secondary batteries, thereby exhibiting excellent electrochemical performance. BRIEF DESCRIPTION OF THE DRAWINGS
[0017] Figure 1 This is an SEM image of the one-dimensional vanadium-based nanoscroll prepared in Example 1; Figure 2 This is an SEM image of the one-dimensional vanadium-based nanoscroll prepared in Example 2; Figure 3 This is an SEM image of the one-dimensional vanadium-based nanoscroll prepared in Example 3; Figure 4 SEM image of the sample prepared in Comparative Example 1; Figure 5 SEM image of the sample prepared for Comparative Example 2; Figure 6This is a comparison chart of the potassium storage performance of the samples prepared in Example 1, Example 2 and Comparative Example 1 and the original V2C MXene sample. DETAILED DESCRIPTION
[0018] To further clarify the objectives, technical solutions, and advantages of the present invention, the present invention is further described below with reference to the accompanying drawings, examples, and comparative examples. All chemicals used in the examples and comparative examples, except for MXene, were purchased from Maclean. It should be understood that the specific examples described herein are intended only to illustrate the present invention and are not intended to limit the present invention. Example 1
[0019] (1) Place 0.1 g of V2C in 30 mL of octadecylamine solution and stir with a magnetic stirrer until the mixture is uniform. (2) No additional raw materials are added; (3) The mixed solution obtained above was transferred into a 50 mL reactor, sealed and placed in a vacuum drying oven at 180 o C reaction for 48 h; (4) Wash the precipitate obtained in step (3) with anhydrous ethanol three times; (5) Dry the precipitate obtained in step (4) in a vacuum drying oven for 24 h. Example 2
[0020] (1) Dissolve 2 g of tetradecylamine in 15 mL of alcohol, stir to dissolve, then add 15 mL of water and stir with a magnetic stirrer until completely mixed. (2) Place 0.5 g of V2C in the above solution and stir with a magnetic stirrer to mix thoroughly. (2) No additional raw materials are added; (3) The mixed solution obtained above was transferred into a 50 mL reactor, sealed and placed in a vacuum drying oven at 150 o C reaction for 72 h; (4) Wash the precipitate obtained in step (3) with anhydrous ethanol three times; (5) Dry the precipitate obtained in step (4) in a vacuum drying oven for 24 h. Example 3
[0021] (1) Place 0.05 g of V2C in 30 mL of octadecylamine solution and stir with a magnetic stirrer until the mixture is uniform. (2) Add 0.05 g of sulfur powder and stir with a magnetic stirrer until the mixture is uniform; (3) The mixed solution obtained above was transferred into a 50 mL reactor, sealed and placed in a vacuum drying oven at 200o C reaction for 10 h; (4) Wash the precipitate obtained in step (3) with anhydrous ethanol three times; (5) Dry the precipitate obtained in step (4) in a vacuum drying oven for 24 h. Comparative Example 1
[0022] (1) Place 0.1 g of V2C in 30 mL of octadecylamine solution and stir with a magnetic stirrer until the mixture is uniform. (2) No additional raw materials are added; (3) The mixed solution obtained above was transferred into a 50 mL reactor, sealed and placed in a vacuum drying oven at 130 o C reaction for 72 h; (4) Wash the precipitate obtained in step (3) with anhydrous ethanol three times; (5) Dry the precipitate obtained in step (4) in a vacuum drying oven for 24 h. Comparative Example 2
[0023] (1) Place 0.05 g of V2C in 30 mL of octadecylamine solution and stir with a magnetic stirrer until the mixture is uniform. (2) Add 0.05 g of sulfur powder and stir with a magnetic stirrer until the mixture is uniform; (3) The mixed solution obtained above was transferred into a 50 mL reactor, sealed and placed in a vacuum drying oven at 180 o C reaction for 96 h; (4) Wash the precipitate obtained in step (3) with anhydrous ethanol three times; (5) Dry the precipitate obtained in step (4) in a vacuum drying oven for 24 h.
[0024] Figure 1 、 Figure 2 and Figure 3 The SEM images of Example 1, Example 2 and Example 3 respectively prove that by changing the raw material ratio, solvent type and hydrothermal reaction temperature within a limited range, a nanoscroll structure with uniform morphology can be obtained. Figure 4 and Figure 5 The SEM images of Comparative Examples 1 and 2 illustrate that the morphology and structure of the materials change when the hydrothermal reaction temperature is lowered or the temperature is increased and the reaction time is prolonged. Comparison of the SEM images of the comparative examples and the examples shows that the synthesis conditions play a key role in the morphology and uniformity of the synthesized products. Potassium ion battery assembly and testing
[0025] The vanadium-based nanoscroll active materials prepared in the examples and comparative examples of the present invention, acetylene black, and sodium carboxymethyl cellulose were mixed in deionized water at a mass ratio of 7:2:1 to form a uniform slurry, which was then coated onto copper foil. The slurry was then vacuum-dried at 110°C for 11 hours to serve as the negative electrode for a potassium-ion battery. Potassium metal was used as the counter electrode to form a button-type potassium-ion half-cell. Battery assembly was then performed in an Ar atmosphere glove box.
[0026] The original V2C MXene and the samples obtained in Example 1, Example 2, and Comparative Example 1 were assembled into potassium ion half-cells, and the charge-discharge cycle test was carried out on the test instrument with a test voltage range of 0.01~3 V. Figure 6 As shown, at 1.0 Ag -1 After 80 cycles at a current density of , the potassium storage capacity of the samples in Example 1 and Example 2 was approximately 160 mAh g -1 and 135mAh g -1 , significantly higher than that of Comparative Example 1 and the original V2C MXene. This demonstrates that this technical solution leverages the compositional and performance advantages of V2C MXene. The prepared sample possesses a nanoscroll structure while fully leveraging its electrochemical performance advantages, such as significantly improved potassium storage capacity.
[0027] The above-described embodiments merely represent a number of embodiments of the present invention. While the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the patent. It should be noted that a person skilled in the art would be able to make numerous variations and improvements without departing from the spirit of the present invention, and these variations and improvements fall within the scope of protection of the present invention. Therefore, the scope of protection of the patent for this invention shall be determined by the appended claims.
Claims
1. A vanadium-based MXene-derived one-dimensional nanoscroll material, characterized in that: The one-dimensional nanoscroll structure has a diameter of nanometers and a length of micrometers.
2. A method for preparing the vanadium-based MXene-derived one-dimensional nanoscroll material according to claim 1, characterized in that: Use the following steps: (1) Take multilayer V2C MXene powder as the derivative precursor phase; (2) preparing a reaction solvent, wherein the reaction solvent is mainly an octadecylamine solution or a tetradecylamine solution; (3) Add the V2C MXene powder in step (1) to the reaction solvent in (2) and stir at room temperature for 2-24 h; (4) Add the desired non-metal source raw material to the solution obtained in step (3) and o C and stir for 2-24 h; (5) Transferring the mixed solution obtained in step (4) into a reactor and heating the reaction; (6) washing the precipitate obtained in step (5) to remove the residual solution; (7) Drying the precipitate obtained in step (6) to obtain a V2C MXene-derived one-dimensional nanoscroll material.
3. The method according to claim 2, characterized in that The octadecylamine solution in step (2) is a commercially available chemical solvent; the tetradecylamine solution is prepared by dissolving the tetradecylamine reagent in a mixed solution of anhydrous ethanol and deionized water, wherein the concentration of the tetradecylamine solution is 0.05-0.1 g / mL, and the volume ratio of anhydrous ethanol to deionized water is 0.5-1.
4. The method according to claim 2, characterized in that The non-metallic source described in step (4) is a sulfur source, a selenium source, etc., and the raw materials are sulfur powder, selenium powder, etc.
5. The method according to claim 2, characterized in that The reaction temperature in step (5) is 150-200 o C, the reaction time is 10-72 h, and heating is carried out in a forced air drying oven or a vacuum drying oven.
6. The method according to claim 2, characterized in that The washing solvent in step (6) is alcohol.
7. The method according to claim 2, characterized in that The drying temperature in step (7) is 60 o C dry for 12-48h.
8. The method according to any one of claims 2 to 7, characterized in that: The specific preparation method adopts the following steps: (1) Take 0.05-0.5 g of vanadium-based MXene and place it in 30 mL of octadecylamine solution, or 30 mL of a mixture of anhydrous ethanol and water in tetradecylamine, with a tetradecylamine concentration of 0.05-0.1 g / mL and a volume ratio of anhydrous ethanol to deionized water of 0.5-1; (2) adding sulfur powder or selenium powder in a corresponding stoichiometric ratio to the mixed solution in (1), or adding no additional non-metallic source; (3) Transfer the mixed solution in step (2) into the reactor, seal it and place it in a drying oven at 150-200 o C temperature range for 10-72 h; (4) Wash the obtained precipitate with anhydrous ethanol 3-6 times to remove the residual solution; (5) The precipitate obtained in step (4) was heated to 60 o C for 12-48 h.
9. A vanadium-based MXene-derived one-dimensional nanoscroll material prepared by the method of claims 1-8, characterized in that: The one-dimensional nanoscroll material has a diameter of several tens of nanometers and a length of several to more than ten micrometers.
10. An application of the vanadium-based MXene-derived one-dimensional nanoscroll material according to claim 1, characterized in that: It is used in the electrochemical field as a negative electrode material for secondary batteries.